Preparation of tertiary amines



Oct. 7, 1969 R. L. WAKEMAN ETAL PREPARATION OF TERTIARY AMINES FiledAug. 17, 1965 ALPHA OLEFIN 2 1 2 m- I'rap eg' ate? 1! P' f r--1 ReactionZone No. l i- HBr Abihrdrobrominator or- Generator er Secondary Amine YSolvent H2801;

8 sulfates Scrubber t i 7 Metal Reaction Zone No. 2 Y Aminator 2 ideVapor- Solvent izer Makeu; 4

131- Neutralizer liquic x N *L' Aqueous Crude Tertiary Metal BromideAmine I C1 +Br H2O 2 2 4 Metal Clarifier C1 Cl" lorin- Bromide ator*Evaporator or Still I or Dryer V J L Refined Tertiary waste Amine Note:The HBr Generator is a Choice of either 3 Bromine-Hydrogen or ASalt-Acid System United States Patent 3,471,562 PREPARATION OF TERTIARYAMINES Reginald L. Wakeman, Philadelphia, Pa, and Edward Griflin Shay,Belle Mead, N.J., assignors to Millmaster Onyx Corporation, New York,N.Y., a corporation of New York Filed Aug. 17, 1965, Ser. No. 480,394Int. Cl. C07c 85/00 US. Cl. 260583 5 Claims ABSTRACT OF THE DISCLOSURE Aprocess for making long chain, unbranched, aliphatic tertiary amineswhich comprises the steps of reacting a straight chain alpha olefinhaving 6 to 24 carbon atoms with hydrogen bromide at a temperature ofabout 0 C., or below, to form l-bromo alkane, reacting the l-bromoalkane, in liquid phase, with an excess of alkyl amine to form atertiary amine hydrobromide, treating the tertiary amine hydrobromidewith a metal hydroxide solution to liberate the free tertiary amine andto form bromide salts, producing hydrogen bromide from the bromidesalts, and then recycling the hydrogen bromide to react with additionalstraight chain alpha olefins of the above type.

The object of the present invention is the preparation of long chainunbranched aliphatic tertiary amines of low cost.

Tertiary amines which possess useful and valuable properties are wellknown to the art. They are, however, rather costly, being usuallyprepared from naturally occurring fatty alcohols such as are present inspermaceti and the like, or otherwise from fatty acids or their estersby reduction, as by hydrogenation. Methods well known to the art forpreparing the amines consist, in general, of such processes asconverting the fatty alcohols to their halides, followed by reaction ofthese halides with secondary amines to form tertiary amines as theirhydrohalides from which they can be recovered by treatment With alkalisolution; or by such stepwise processes as the saponification ofnaturally occurring fats with ammonia; .the dehydration of the ammoniumsoaps to the amides; the further dehydration of the amides to thecorresponding nitriles; followed by hydrogenation to produce mixtures ofmainly primary and secondary plus some tertiary long chain amines whichmay be separated by fractional distillation into suitable fractions, oneof which is the preferred primary amine; this in turn is followed byalkylation, as by means of formaldehyde and formic acid by a modifiedMannich reaction; or by reaction with an alkyl halide such as methylchloride to yield tertiary amine hydrohalides from which the free aminescan be obtained by adding a solution of caustic alkali. By this meansare obtained tertiary amines containing one long hydrocarbon radicalplus two short radicals such as methyl, along with more or less tertiaryamine containing two long chain and one short chain radicals.

These tertiary amines which may be either mixtures containing a wideseries of homologous amines, or as the result of distillation a narrowerrange of such homologs, or where desired a segregated amine of adefinite chain length, may then be further processed by reacting themunder suitable conditions as, for example, with an oxidizing agent suchas hydrogen peroxide, an organic peroxide, or ozone and the like, toproduce amine oxides. Such oxidation processes are well known to the artand are in use for the manufacture of certain surface active agents ofcommercial value. The tertiary amines may also be processed by treatingthem with alkylating agents such as methyl chloride, ethyl bromide,benzyl chloride,

dimethyl sulfate and the like, in which case quaternary ammonium saltsare formed. These compounds are valuable articles of commerce with awide range of applications, including such uses as sanitization anddisinfection, fabric softening and the prevention of the accumulation ofstatic electric charges. The tertiary amines may also be used to prepareamphoteric surface active agents of the betaine type as, for example, byreaction with chloro acetic acid or its salts and the like. Other usesfor these fatty tertiary amines will be readily apparent to thoseskilled in the art.

These operations, because of their complexity, are necessarily costly.Since the raw materials either naturally occurring or synthesized arealso relatively expensive, the end products often have been of limitedcommercial applicability, solely for economic reasons.

This invention proposes to reduce these costs substantially by employingmaterials of low cost; namely, straight chain alpha olefins obtained,for example, from the cracking of waxes, or derived synthetically fromthe condensation of ethylene as, for example, by the Ziegler process, orby other methods now in commercial use. The preferred range of chainlengths for the synthesis of tertiary amine-s of wide commercialapplicability is from 6 to 24 carbon atoms.

In addition to the mono-tertiary amines of this invention, di-tertiaryamines may also be prepared in the same manner from alpha-omegadi-olefins.

Straight chain olefins are to be preferred because the surface activeproperties of branched chain compounds are inferior for a givenmolecular weight to those of their straight chain isomers. Alpha olefinsare to be preferred because substitution in the 1-position yields morestable and more effective products.

It is therefore desirable to employ the aforesaid straight chainolefins, although up to about 20% of branched chain compounds orcompounds substituted in other than the 1-position may be tolerated.

In the first stage of the process of this invention, the olefins arereacted with anhydrous hydrogen bromide under conditions suitable forthe formation of l-bromoalkanes, for example, in the presence of aninitiator such as an organic peroxide and at low temperatures, or byirradiation. Since bromine and its derivatives are costly, it isnecessary to recover and recycle essentially all of the hydrogen bromideemployed. The process described herein accomplishes this purpose, aswill appear hereinafter. As will also appear, the reaction conditionshave been selected to produce essentially only the l-bromoalkanes.

The alkyl bromides so obtained are then converted into suitable tertiaryamines as, for example, the alkyl dimethyl amines, by reacting themunder pressure with an excess of dimethyl amine at temperatures rangingfrom to 250 C., but preferably at 100 to C. over a period of from 1 to10 hours until no further reaction occurs; this point may be determinedby argentometric titration. Preferably a quantity of a polar solvent isincluded in the reaction mixture to increase the reac' tion rate.

On completion of reaction, the unreacted excess of dimethyl amine orother amine used in the process is recovered for reuse by distillationand water is added to dissolve the tertiary amine hydrobromide formed,with or without the addition of alcohol or the like to facilitate clearseparation.

The amine hydrobromide solution is removed and upon addition of therequired amount of alkali to liberate the free amine from its salt, theproduct separates as an oily layer. This may be clarified as byfiltration to remove gross dirt, and it may be dried as by heating todrive off the small amount of dissolved or dispersed water, or it may beused in its crude form. For the sake of good color, it is desirable torid it of such foreign matter.

The crude tertiary amine may be rectified by distillation to removesmall amounts of low-boiling material and the still bottoms if anespecially pure amine is desired; or it may be fractionally distilled toobtain amines of narrow range chain length.

The drawing, FIGURE 1, illustrates a flow chart embodying the novelfeatures of the process. This chart illustrates graphically the sequenceof steps of the process in producing straight chain alkyl tertiaryamines, starting with straight chain alpha olefins preferably havingfrom 6 to 24 carbon atoms, through the addition of HBr, the reaction ofthe alkyl bromide formed with a suitable secondary amine to form atertiary amine hydrobromide; the recovery of the excess aminating agent;the removal and recovery of the combined hydrobromic acid; and theregeneration of hydrogen bromide.

The flow chart indicates how hydrogen bromide is prepared and introducedinto a reactor where it reacts with the olefin. It also indicates howthe small amount of excess or eflluent HBr gas is trapped and removedfor recycling. The chart also illustrates how the alkyl bromide may bewashed to remove free or dissolved or occluded HBr to be recycled.

It further illustrates how the alkyl bromide so formed is introducedinto a second reactor where it is reacted with a secondary amine,preferably in the presence of a polar solvent, desirably a mutualsolvent for the alkyl bromide and the secondary amine. The chart alsoshows how the unreacted excess secondary amine along with the solvent isdistilled from the reaction zone, and how the amine hydrobromide is thenconverted to free amine and to aqueous inorganic bromide salt by theaddition of caustic alkali; from which mixture a further quantity ofsecondary amine may be distilled and recovered and added to the reactionzone fraction to be reinforced and recycled. The flow chart furthershows how the aqueous and oily phases are separated so that the tertiaryamine product may be clarified, dried or distilled to the degree ofpurity desired. It also shows how the inorganic salt layer may be tappedoff into either of alternative vessels, to be concentrated to a liquoror slurry, or dried to solid salt; or otherwise, to be treated withchlorine gas to yield liquid bromine and by-product inorganic chloride.

Finally, the chart illustrates how the recovered combined bromidefractions are treated to regenerate anhydrous hydrogen bromide gas; inthe first case by reacting the inorganic bromide salt with sulfuric acidand cleaning the generated hydrogen bromide gas; or in the second caseby burning vaporized bromine together with hydrogen gas to formanhydrous hydrogen bromide, in apparatus which is known to the art andwhich is commercially available. In either case, the regeneration isconducted with a minimum of loss and consequently with a negligibleexpenditure for hydrogen bromide except for the cost of processing, aswell as with a minimum of nuisance from corrosive fumes andobjectionable waste residues.

The hydrobromination process is suited to batchwise methods, and also tocontinuous operation by means of suitable apparatus.

The following examples illustrate in greater detail the successive stepsof the process of this invention.

Example I A closed, agitated and jacketed glass-lined 20 gallon reactorwas fitted with a sparger, and also with a vent pipe connected to abubbler and an absorber containing caustic soda solution, for trappingany escaping HBr gas.

The reactor was charged with 61.5 pounds of a commercially obtainedmixture of alpha olefins consisting of 75% of l-tetradecene and 25% ofl-hexadecene, plus 005 pound of a 60% solution of methyl ethyl ketoneperoxide in an inert solvent. The mixture was cooled to 5 C. and a slowstream of freshly generated anhydrous hydrogen bromide was bubbledthrough it, until a rise in temperature indicated the inception ofexothermic hydrobromination.

Thereafter, hydrogen bromide was fed in as fast as possible whilemaintaining a reaction temperature of about 3 C. by circulating arefrigerant through the jacket of the kettle.

After two hours, the reaction rate diminished, and the flow of HBr gaswas reduced until only a trace of it escaped, to be trapped in theabsorber.

The reaction was continued for two hours longer, when no more HBrappeared to be absorbed, and the specific gravity of the charge hadincreased from 0.770 to 1.013.

A sample was washed and dried and assayed by titration with KBr-KBrOmixture, as described in The Estimation of Unsaturation Content ofPetroleum Products by A. W. Francis in I.E.C., 18 (8), pp. 821-822.

Less than 0.1% of residual olefin was found.

The alkyl bromide product was washed free of acid and dried. Thewashings were combined with the trapped HBr from the effiuent absorberand set aside for recovery and reuse.

The product amounted to 86 pounds, or essentially the theoretical yield.It was assayed by saponification with alcoholic potash during 5 hours atthe reflux; and also by reaction with a secondary amine to form atertiary amine hydrobomide, followed by argentometric titration. Bothmethods indicated more than 98.5% of conversion from olefin to bromideof which about 90% was a mixture of l-bromotetradecane andl-bromohexadecane.

Example II Using the same procedure as in Example I, l-hexene, l-octene,l-decene, l-dodecene; a mixture of l-hexadecene and l-octadecene; abroad band C to C mixture; a petroleum derived mixture of alpha olefinsranging from C to C and alpha olefins derived from the dehydration ofprimary alcohols of C to C chain length; were all successively reactedto prepare the corresponding bromides in similar yield and quality.

In the case of l-hexadecene and the higher homologs, the temperature wasallowed to rise towards the end to prevent solidification of thereaction mass.

Example III The process according to Example I was carried out,substituting for methyl ethyl ketone peroxide, catalytic amounts ofbenzoyl peroxide.

The corresponding bromides were obtained in high yield and quantity fromthe olefins used in Examples I and 11.

Example IV One mol of the C to C alkyl bromides of Example I and threemols of a 25 to 30% solution of dimethyl amine in isopropanol werecharged into a pressure reactor and heated under agitation at to C. fora period of five hours until reaction to alkyl dimethyl aminehydrobromide was complete.

The excess of dimethyl amine and isopropanol was distilled off. Causticsoda solution in slight excess was added to the residue and theremaining excess dimethyl amine was distilled off.

The recovery of unreacted dimethyl amine and isopropanol amounted to90%. It was set aside for recycling after fortification with make upamine and alcohol.

The brine was tapped off and combined with the bromide effiuents andwashes of Example I for recovery of hydrogen bromide as described inExamples VII and VIII below. The mixed bromides were assayed bytitration and found to contain about 98% of the hydrogen bromide used inthe hydrobromination.

The alkyl dimethyl amine product was washed and clarified. The yield wasessentially the theoretical.

On distillation in vacuo at 7 mm. pressure, and to a top temperature of190 to 200 C., after removing a small forerun, a refined amine of highquality was obtained in overall yield of 82%, or weight for weight ofthe starting olefin.

Example V The alkyl bromides of Example III were reacted with dimethylamine as in Example IV, to obtain the corresponding crude alkyl dimethylamines in essentially the theoretical yield and high quality.

Refined amines were obtained after vacuum distillation as described inExample IV.

The brines were collected and used to regenerate hydrogen bromide gasfor the next run.

Example VII The brine and other bromide liquors from Example IV werecombined and charged into a chlorinator, wherein chlorine gas wasbubbled through to liberate liquid bromine, which settled to the bottom,and to form sodium chloride. The bromine was tapped OE, and the brinewas further treated by a degree of steam distillation, whereby most ofthe dissolved bromine was recovered, the dissolved chlorine beingremoved in the first runnings. The combined bromine layers were driedand stored.

Proportional amounts of bromine vaporized therefrom and of hydrogen werefed to a combustion chamber or furnace wherein they burned to formanhydrous hydrogen bromide, at a rate variable at will for the processof hydrobromination as described in preceding examples.

Overall recovery of hydrogen bromide was about 95% for the entire cycle.Additional make up bromine was burned in the same manner to provide thenecessary amount of hydrogen bromide for complete hydrobromination.

Calcium or potassium bromide brine may be regenerated in the samemanner.

Example VIII The calcium bromide brine and washings from the processaccording to Example V was concentrated by evaporation to 70% strength.It contained about 98% of the bromine used in the process.

The concentrate was charged into a jacketed glasslined reactor.Concentrated (i.e. 98%) sulfuric acid was added gradually while heatingthe charge to 110 C. until the evolution of HBr began; this wasconducted to the hydrobromination vessel, through a dephlegmator toreturn aqueous hydrobromic acid to the generator, and through a brominetrap. The operation according to the process of Example I was carriedout, and the rate of hydrogen bromide production was controlled byvarying the rate of addition of sulfuric acid and the rate of heating ofthe generator, up to 130 C. Make up bromide was added as required 'froma reserve store to ensure completion of the hydrobromination.

When the reaction with olefin wascomplete, the generator was heatedfurther to about 150 C. and under gradually reduced pressure, to about26 inches of vacuum. A quantity of hydrogen bromide as aqueous solutionwas recovered and set aside for reuse.

The overall materials balance indicated 95 recovery of the bromidecharged per batch.

Sodium or potassium bromide may be used instead of calcium bromide.

From the residue, after cooling, a part of the sulfuric acid at about70% concentration may be recovered by means of a solid-bowl centrifugal.The metal sulfate or bisulfate cake is discarded.

Instead of concentrating the bromide brine, it may be sprayortunneldried, for addition to recovered 70% sulfuric acid; make up acidthereafter required would be of 98% grade.

Example DC A continuous countercurrent Pyrex reactor was constructed,the reaction chamber consisting of a Graham condenser with 17 coils andabout 40 cm. in length. The top of the column was fitted with a T toadmit a dropping funnel for the charge, and a vent for eflluent gas. Thebottom of the column contained a gas dispersion tube for admitting HBrgas from a cylinder, and a stopcock for removing the product. I

The jacket was cooled with circulated isopropanol at 5 to --10 C.

l-dodecene was charged into the dropping funnel, plus 0.25 volumepercent of a 60% solvent solution of methyl ethyl ketone peroxide. Thecoils were filled with the dodecene which was allowed to chill; HBr gaswas then passed in countercurrently at a rate less than enough to bubbleout at the top. The rates of addition of charge and of efilux of productwere regulated to maintain the column full at all times, and to removethe product at an optimum rate.

At a throughput of 94 ml. per hour, the eifluent assayed more than 99%as alkyl bromide, containing about 94% of l-bromododecane.

For ease of control, we prefer to use HBr generated by burning hydrogenand bromine with this system.

Example X In the continuous countercurrent reactor of Example IX, deceneand C to C olefins were hydrobrominated in the same manner.

Example XI The continuous hydrobromination as described in Examples IXand X was also carried out, substituting benzoyl peroxide for methylethyl ketone peroxide, using about 0.5% on the weight of the olefin,with equally good results, approaching or attaining 100% conversion.

Example XII The continuous, countercurrent reactor of Example D( wasused for the hydrobromination without the addition of a peroxidecatalyst, but instead by irradiating the column with a Hanoviaultraviolet lamp.

At a throughput of 76.5 ml. per hour, l-dodecene yielded a bromide of98.5% conversion.

Example XIII In the same manner as in Example XII, l-octadecene wasirradiated at 19 to 22 C. to 99% conversion to the bromide; hexadecylbromide was obtained in 99.5% yield at 5 to 19 C., and tetradecylbromide in 100% yield at about 6 C., without solidification, from thecorresponding alpha olefins. All cited temperatures are in the coolingliquor in the jacket.

l-hexadecene-l-octadecene mixture was reacted with hydrogen bromide inthe same manner. C to C olefins were also reacted, at a temperature ofabout 25 C.

Example XIV The alkyl bromides obtained in the above examples werereacted with diethyl amine instead of dimethyl amine. Reaction wascomplete within six hours, yielding the corresponding alkyl diethylamines.

7 Example XV The alkyl bromides as obtained in Examples I to III and IXto XIII were reacted with diethanolamine for six hours to yield thecorresponding alkyl diethanolamines.

Example XVI The alkyl bromides as obtained in Examples I to III and IXto XIII were reacted with morpholine for a period of about eight hoursto yield the corresponding N-alkyl morpholines.

Example XVII One mol of the C to C alkyl bromide of Example I wasreacted for six hours at 110 C. in a pressure vessel with about eightmols of 30% monomethyl amine in isopropanol. The excess methyl amine andthe alcohol were stripped off, and one mol of caustic soda solution wasadded to form sodium bromide and C to C alkyl methyl amine. Furthermethyl amine was distilled off.

To the residual charge, a second mol of the alkyl bromide was added inan equal volume of isopropanol, and the heating was continued for afurther period of hours. The alcohol was stripped off and the productwas treated with one mol of aqueous caustic to neutralize thehydrobromide.

The combined brines were segregated for recovery as hydrogen bromide.The product obtained was di(C to C alkyl) methyl amine.

In a similar manner, the alkyl bromides from Examples II, III, IX, X andXIII were converted to the corresponding di-alkyl methyl amines.

Example XVIII The distilled C to C alkyl dimethyl amine of Example IVwas titrated with standard acid and was found to have a combining weightof 257 (theory=250).

One hundred and thirty-one grams or 0.51 mol of the amine were reactedwith 83.3 grams or 0.50 mol of benzyl chloride in 215 grams of water byheating to 90 C. for one hour, at the end of which time the reaction wascomplete as determined by argentometn'c titration. The solution was50.5% in concentration as C to C alkyl dimethyl benzyl ammoniumchloride.

The product was tested bacteriologically by the Official PhenolCoefficient Method of the United States Department of Agriculture,against Salmonella typhosa and Staphylococcus aureus.

For comparison, a sample of ETC-824, an alkyl dimethyl benzyl ammoniumchloride in which the alkyl distribution is 60% C 30% C C and 5% C wastested in the same manner. They compared as follows:

Phenol Coefficient at 20 C. vs.

Sample S. aurcus S. typhosa Example XVIII 875 584 ETC-824 900 544 Eachexhibited a hard water tolerance of 550 parts per million by theChambers modification of the Weber and Black method (vide George F.Reddish, Antiseptics, Disinfectants, Fungicides, and Chemical andPhysical Sterilization, 2nd edition (1957), page 185).

Example XIX temperature of 100 to 110 C. This temperature was maintainedfor three hours, at the end of which time argentometric titrationindicated that the reaction was complete.

The product, the hydrochloride of C -C alkyl dimethyl betaine, was thenneutralized in a second agitated flask containing two equivalents ofcaustic soda in aqueous solution, to which it was added while agitatingand cooling. The final product, which is the sodium salt, had a pH of6.0. It is an effective foaming and wetting agent, and is amphoteric incharacter, containing both a carboxyl and a quaternary ammonium group.

Example XX One hundred grams of the distilled C -C alkyl dimethyl amineof Example IV was dissolved in grams of isopropanol and 50 grams ofwater in an agitated flask equipped with a reflux condenser and adropping funnel charged with 50% hydrogen peroxide. The solution washeated to 40 C., and 34 grams of hydrogen peroxide was added while thetemperature was maintained between 40 and 80 C. by cooling and heatingas required. The reaction was continued for several hours until themixture first became homogeneous and then gave a clear solution inwater. Heating was continued until the excess hydrogen peroxide wasdecomposed. The solution was diluted with water to 15% strength as C Calkyl dimethyl amine oxide.

Tested at 1.0% and at 0.1% concentration, the product showed excellentfoam stability when tested by methods well known to the art.

Example XXI A mixture of two parts of di-octadecyl methyl amine and onepart of di-hexadecyl methyl amine obtained by the method of Example XVIIwas quaternized with dimethyl sulfate as follows, for the purpose ofpreparing a fabric softener. 64 parts by weight of the amines, 20 partsof isopropanol, 5 parts of water and 3 parts of sodium bicarbonate wereheated together with agitation at 80 C., and the theoretical amount,about 15 parts of dimethyl sulfate was added slowly; the temperature wasmaintained at 80 to 100 C. until the reaction was essentially complete,as evidenced by the decrease in titrable amine.

The mixture was cooled to 60 C. and was filtered to clarify it. Waterwas added to adjust the concentration to 75% as di-(C C alkyl) dimethylammonium methosulfate, by Epton titration.

The product was tested against similar, commercial household softenersof the di(hydrogenated tallow) dimethyl ammonium chloride ormethosulfate type and found to be at least as effective, when applied tounfinished terry cloth toweling in the final rinse in a householdautomatic washing machine. In each case the amount of softener used wassufficient to deposit 750 parts per million on the weight of the fabricby total exhaustion.

Instead of dimethyl sulfate, methyl chloride or diethyl sulfate may beused as the quaternizing agent.

The above examples have been .cited to describe the invention and arenot intended to limit it. It has been shown that alpha olefins, whetherderived from petroleum, as by thermal cracking of waxes, orsynthetically by the condensation of ethylene, or otherwise, have beenreacted with hydrogen bromide catalytically under suitable conditions toyield alkyl bromides which are almost entirely l-bromides; that thisreaction is feasible either in batch or continuous processes; that byvirtue of skillful and ingenious cycling and recycling, bromine orhydrogen bromide may be employed to this end with a very minimum of lossand therefore of cost except for process handling; and that such cyclingis not only efficient but almost totally devoid of the nuisance orhazard of toxic or corrosive fumes.

It has also been shown that the alkyl bromides so obtained are ofexcellent quality. It has further been demonstrated that the useful andvaluable tertiary amines obtained therefrom compare favorably withsimilar but relatively more costly amines such as may be and are derivedfrom fatty alcohols or fatty acids by involved processes. It has alsobeen shown that the said amines can be prepared from the bromides withease and that in their preparation only a very small amount of therequired excess of reactants and solvents is left unrecoverable.

The process of this invention is therefore a novel, useful andeconomical one for synthesizing products of commercial utility andvalue, and most important from the commercial viewpoint, at low cost andin a compact plant.

We claim:

1. The process of making straight chain alkyl tertiary amines whichcomprises the steps of reacting a straight chain alpha olefin having 6to 24 carbon atoms, in liquid phase, with anhydrous hydrogen bromide toform l-bromo alkane, reacting the l-bromo alkane, in liquid phase, withan excess of an amine selected from the group consisting of monoalkylamine, dialkyl amine and dihydroxyalkyl amine to form a tertiary aminehydrobromide, treating the tertiary amine hydrobromide with a metalhydroxide solution to liberate the free tertiary amine and form bromidesalts, recovering the bromide salts and producing hydrogen bromidetherefrom for reacting same with additional straight chain alpha olefin.

2. The process of making straight chain alkyl tertiary amines as definedin claim 1 wherein the recovered bromide salts are reacted with sulfuricacid to form anhydrous hydrogen bromide and reacting said hydrogenbromide with additional straight chain alpha olefin.

3. The process of making straight chain alkyl tertiary amines as definedin claim 1 wherein the aqueous solution of recovered bromide salts isreacted with chlorine to generate free bromine, reacting the brominewith hydrogen to form anhydrous hydrogen bromide, and reacting saidhydrogen bromide with additional straight chain alpha olefin.

4. The process of making straight chain alkyl tertiary amines as definedin claim 1 wherein the l-bromo alkane is reacted with an excess ofdimethyl amine at a temperature from to 250 C. over a period of 1 to 10hours, in the presence of a polar solvent and recovering unreacteddimethyl amine for reuse in the process.

5. The process of making straight chain alkyl tertiary amines as definedin claim 1 wherein the alpha olefin is selected from the group ofl-octene, l-decene, l-dodecene, l-hexadecene, l-octadecene,l-tetradecene, an alpha olefin derived from the dehydration of primaryalcohols of C to C chain length, a petroleum derived mixture of alphaolefins having C to C chain lengths, and mixtures thereof.

References Cited UNITED STATES PATENTS 3,401,203 9/1968 Kraiman et a1.260-583 2,078,582 4/1937 Nafash. 2,172,822 9/1939 Tamele et al.

OTHER REFERENCES Groggins, Unit Processes in Organic Synthesis, Mc-Graw-Hill, New York, third edition (1947), pages 227 and 228.

CHARLES B. PARKER, Primary Examiner R. L. RAYMOND, Assistant ExaminerUS. Cl. X.R. 260-663

